Method of producing impregnating compositions



Patented Jan. 23, 1940 mrrnon or monuomo momma I oomosmons Bndolf Kern, 0schats, Germany, assignor to the flrm .Ch Baumh emische l'abrik R.

Oschatx-Zscholiau, Ger

' mandltgesellschaft. many eier Koms. Drawing. Application April 15, me, Serial No. 74,893. In Germany August 6, 1880 a cum. (cl. 134-18) My invention relates to improvements in dispersed substances and the process for making such substances as well as the fabrics to the fibres .of which the substance is absorbed.

5 It has, heretofore been proposed to render fabrics water-proof by impregnating the same with soaps of multlvalent metals. Ordinarily the fabric is first placed in a bath of alumina and then in a soap bath, or .vice versa. In this connecw tion the soap bath, which has no water-proofing eifect in itself, may also contain water-insoluble substances, such as wax, parailin, or the like. In this process, therefore, two or more baths are required. In another process the fabrics are 16 treated in a preformed organic solution of aluminum soaps in solvents. This process, however, is expensive and uneconomical owing to the loss of solvent. To avoid these disadvantages it has also been proposed to treat the fabric in aqueous suspensions of aluminum soaps formed merely by a simple stirring process. This method, however, has not; only the disadvantage of instability of the liquors but also that of irregularity of the impregnation; Since in the ordinary way of Q production the aluminum soaps occur in theform of comparatively large particles, the impregnation is irregular, and these comparatively large structures are unable topenetrate. the fabric. For this reason the impregnation is unsatgo isfactory. The aluminum soaps adhere to'thefabric merely superficially and are easily ren dered ineffective when the fabric is in use. Ihere is also obtained an inferior finish, and the fabric is coarse to the touch.

3 The object of the present improvements is to provide a process which. is free of the said obiections, and with this object in view my invention consists in manufacturing emulsions which are capable of resisting storage, transport and g frost and are simple and economical to handle.

In the following there will be described the composition of the emulsion, its production, and the manner in which the process is-employed.

l. The emulsions consist of soaps of multi- I valent metals, and more particularly of alumi'-' fatty acids may be saturated or unsaturated or also semi-drying or drying fatty'acids.

- 2. The emulsions contain a water-insoluble I water-proofing substance asdispersed constitu ent. Substances .of this nature are parafln, Paraffin oil. mineral oil, vegetable oils and fats. resins, animal, vegetable or mineral waxes and latex, either singly or admixed.

. 3. A protective colloid which is soluble in water 5 and swells. Substances of this kind are glue, gelatine, starch, dextrin, vegetable slimes, casein, vegetable proteins, carrageon moss or the like.

4. The salt of a multivalent cation, which is added for the purpose of producing the soap of 10. the multivalent metal referred to under 1. This accordingly relates to the salt which is decomposed with the alkaline salt of the fatty acid 9.0- cording to 1. It is necessary to employ more salt than corresponds with the molecular conditions. II

For example, to convert sodium seep into aluminum soap it is necessary to employ not the equivalent amount of aluminum salt, but an excess thereof. This feature was already included in the example given in the original papers filed so August 6, 1930. These features of the compo- .sition represent essential parts of the'emulsions.

Reference'will also be made, however. to an additional feature which in numerous cases serves to enhance the properties of the emulsions. This as relates to 5. The addition of wetting agents of an organic kind, which cause the dispersed components to penetrate more readily into the threads or fabric; Wetting agents of this kind are alco- U hols, ketones, esters, organic bases or salts of the latter. By way of example reference may be made to the following representatives of these groups: ethyl alcohol, n-butanol, cyclohexanol, methyl-cyclohexanon, amyl acetate, pyridine 88 bases and triethanolamine formate. It is common to all of these wetting agents that in contradistinction to the usual'substances of this kind they have no polar group which is capable of entering into a salt with the multivalent 4o :sirable to produce concentrated emulsionafor example those in which the dispersal phase amounts to 10-30% or more of the emulsion.

An essential feature of the emulsions accordingtotheinvention consists in'thefactthat.

these are homogenized, i. e., that the aqueous dispersions or emulsions are forced in positive fashion through narrow slots, apertures or passages, in which connection there occurs a grinding action and in consequence a reduction in the size of the particles of the dispersed component. A machine, which is suitable for producing the emulsion in this fashion, together with its arrangement is described in detail by Otto Lange, in 19 Technik der Emulsionen", 1929 (Berlin), pages 77 to B0. The homogenization itself may take place at different temperatures and is dependent primarily on the viscosity of the product to be homogenized or on the melting point of the 15 dispersed component. The higher the melting point of the oleaginous phase, the greater will be the homogenizing temperature which is required. The advantage of the homogenization is based on two factors. Owing to the small size of the particles the emulsions are extremely re sistant to transport, frost and storage, whilst on the other hand solutions produced from the same are capable of resisting separation or creaming. These powers of resistance, however, do not interfere with the treatment of textile materials, and the small particles are picked up by the fibres and deposited and held in the in terstlces of the materials. This results in a uniform impregnating effect without deterioration of the finish or a dimming effect on the color. The emulsions produced in this way by homogenization reveal in the diluted state a Brownie movement of the molecules.

with regard to the production of the emulsions, it may be stated quite generally that the soaps of the multivalent metals, such as aluminum, are obtained by double decomposition, the aqueous solution of an alkali soap, in the presence of a protective colloid and in the presence of a water-proofing substance, being decomposed, whilst being stirred, with the aqueous solution of a salt of the multivalent metal. As a basis for the process there may be employed finished alkali soaps, or these may be formed during the process by the saponification of a fatty acid with alkali. There is utilised the emulsifying force of the forming or previously formed soap, and through the medium thereof there is emulsified the water-proofing component in wa- 50 ter. The emulsions according to the invention also exhibit the phenomenon that owing to the presence of the salt which forms the multivalent soap, and more particularly, therefore, the aluminum salt, the dispersed component possesses a positive electrostatic charge, and in consequence is attracted by the textile fibres and is fixed thereon. This water-proof state produced in physical-chemical fashion is enhanced by the presence of the soap of the multivalent metal. This soap also assists towards proper adhesion of the impregnation substance.

As has been stated above, prior to the emulsification and homogenization, glue or other mata ter, which will swell when placed in water, is

added to the alkali soap solution as an emulsifying medium, and I am able to use so much oi the swelling matter, such as bone glue, that after mixing a semi-solid product may be obtained. 70 I may also proceed in such a way that parafiin, wax and other water-proofing substances are homogenized with the aluminum soap emulsion, after so much of a swelling medium has been added as an emulsifying medium that after 1 cooling the emulsion, which preferably has been homogenized at an elevated temperature, is solidiiied.

This solid product is able to emulsify with water, and it may be used in the same way as the products referred to above.

Examples 1. 14 kilogrammes of light pine-resin rosin are heated with 3.5 kilogrammes of table parafiin (melting point 52/54 C.) to 80-90 C. In this there are then dissolved, whilst being stirred, 1.5 kilogrammes of 60% soap, which has been produced from palm-kernel oil and earth-. nut oil by saponification with sodium lye. In a separate vessel 2 kilogrammes of gelatine in l pearl form are allowed to soak for 4 hours or longer in 5 kilogrammes of water, and by heating and stirring are then converted to a uniform solution. To this there are added 15.4 kilogrammes of water, both the gelatine solution as well as the water having a temperature of 70 C., and the gelatine solution is then added under agitation to the above mixture of resin, paraii'in and soap. An extremely finely distributed emulsion is obtained. In a third vessel 1.75 kilogrammes of 80% formic acid have been mixed with 6.65 kilogrammes of water, and in this mixture there have been dissolved 1.8 kilogrammes of hydrate of alumina, i. e., 50% aluminum hydroxide, which has been obtained by the precipitation of an aluminum salt with alkali, filtration and gentle drying. There is produced alumina formate, which at 18 C. possesses a spindle weight of 18 B.

The solution of aluminum formate thus obtained is added under agitation to the emulsion produced in the manner described above, and the latter, after being stirred for half an hour, when it has attained a completely uniform condition, is introduced into a three-pump homogenizing machine, such as described in the stated book by Lange, and is homogenized at IO-80 C. under a pressure of 120 atmospheres. This emulsion is allowed to cool either whilst being slowly and steadily stirred or without agitation 5 in a suitable metallic vessel. In the hot state the emulsion is a white viscous substance, and when cold solidifies to form a mass of gelatinous consistency which is capable of being cut. The product thus obtained is employed in the following manner:

In a metallic vessel 5 kilogrammes of the product obtainedin the manner described are mixed under agitation with $40 kilogrammes of water having a temperature of 60 until a uniform and somewhat viscous solution of the emulsion has been formed. In the trough of a padding machine having a capacity of 100 litres there are heated 85 kilogrammes of water to C., and the basic solution is then added so to the remainder of the water through a hairsieve. A wool-gabardine fabric is introduced in the dry condition into this liquor, squeezed out, dried, damped, pressed and cooled and finished of! in the usual manner. This fabric has a 05 proper finish and p0 we a good water-repelling properties.

2. 110 parts parafiln (melting point 52/54 C.)

90 parts parafiln oil, 30 parts montan wax, and

6 parts soya fatty acid (an example of a semidrying fatty acid) are emulsified under agitation with a solution of 2 parts potassium hydroxide (45 B.) and 240 parts water.

To this there are added 35 parts glue in 100 parts water, and into this solution there are stirred 200 M aluminum formate 17 36.), and

. after the emulsion has been evenly distributed iti's homogenized at 150 atmospheres andat a temperature of 55 C. and then allowed to This product is a white plastic substance.

In this example there will be described the use of wetting agents. If for this purpose there is employed an alcohoL-it is incorporated in such fashion thatit is added to the parailn before, during "or after the emulsifying in the soap solution. It is necessary that the wetting agent also be homogenized. When employing pyridine the procedure may be the same, or the pyridine may be added to the aqueous glue solution employed for emulsifying the fatty component. The ratio, for example, is parts cyclohexanol or 6 parts pyridine to 1.000 parts emulsion.

3. 118.4 kilogrammes of table parailin (melting point 52/54 0.), 64 kilogrammes of paramn oil and 50 kilogrammes of the fatty acid of a semidrying oil are melted together, and are emulsified in the hot state by pouring in 75 kilograms of an 8.2% potassium lye. Parallel thereto, after the dissolution of kilogrammes of glue in 50 kilogrammes of water, this solution is mixed with the soap and paraflln emulsion. To enable the chemical decomposition to take place in satisfactory and reliable fashion glue is also added as a protective colloid to the aluminum salt or its aqueous solution, viz., in the following proportions: 28.2 kilogrammes of 80% formic acid are mixed with 212 kilogrammes of water, and in the same there are dissolved 24.8 kilogrammes of hydrate of alumina. To this solution there is added a solution of kilogrammes of glue in 85 kilog'rammes of water. The two reaction compone'nts, i.-e., the aluminum formate solution and the emulsion of glue, soap and paraflin have a temperature of 60 C. The former is now added to the latter under agitation, and homogenization is likewise performed at 60 C. and at 150 atmospheres. After cooling the product is awhite plastic mass. This product, as in Example 1, is dissolved, and a concentration of 20 grammes per litre at 50 C. is sufficient I containing the aluminum salt and the aluminum soap, which solution also contains the protective colloid.

5. The operation as last described in conjunction with the proportions set forth in Example 2 takes the following form:

35 parts glue are dissolved in 100 parts of water, and in this solution there are emulsified 6 parts of a semi-drying fatty acid, for example rape-oil fatty acid. This is then converted to potassium soap by adding 2 parts potassium hydroxide (45 B.) and 240 parts water. To this solution of glue and soap there are added, under continuous agitation, 200 parts aluminum formate (17 B.)' whereupon, by double decomposithe aluminum-salt on the other hand, aluminum thesolution of glue. This mixture is maintained between 55 and 60 C. In an agitating mechanism having a bladed stirrer performing approximately 300-400 R. P. M. there is placed a melted mixture comprising 110 parts paraflin, 90 parts white oil and parts montan'wax. This mixture, which has a temperature of 60-70" C.', is vigorously agitated, and the solution previously produced, as described above, is stirred into the fatty substance. An emulsion is formed, which is thereupon homogenized at a pressure of 150 atmospheres. The product obtained is similar to that'as set forth in Example 2. If desired, the homogenization may be repeated in order still further to reduce the size of the particles. The product is also very suitable in greatly diluted solutions for water-proofing cotton I added a solution comprising 55 parts glue in 350 parts water, likewise having a temperature of 60, and copper soap is formed by adding to this solution whilst stirring 20 parts copper sulphate in 220 parts water. A slightly blue con- -sistent emulsion is formed, which is thereupon homogenized at 60 C., and at 50 C. it is again passed through the machine under a pressure of 200 atmospheres. Cotton fabrics treated with a solution of this emulsion are waterproof and also capable of resisting mildew and rusty stains. I The present application is a continuation in part of my co-pending application, Serial No. 555,148, filed August .4, 1931.

What I claim as new and desire to secure by Letters Patent is:

1 Method of producing impregnating substances for water-proofing textile materials, which consists in emulsifying 110 parts paramn (melting point 52-54 C.), 90 parts paraflln oil, 30 parts montan wax, 6 parts soya fatty acid and 10 parts cyclohexanol in a solution of 2 parts potassium hydroxide of 45 and 240 parts water, adding thereto a solution of parts glue in 100 parts water, adding to the whole 200 parts aluminum formate of 17 B.,

, homogenizing the emulsion at 55 C. and at 150 atmospheres and thereupon allowing the emulsion to cool. i

'2. Method of producing "impregnating substances for water-proofing textile materials, which consists in dissolving 35 parts glue in 100 parts water and emulsifying therein 6 parts rapeoil fatty acid, adding a solution comprising 2 parts potassium hydroxide of 45 B. and 240 parts water, stirring in 200 parts aluminum formate of 17 B., stirring the whole at a temperature of 60 C. into a melted mixture comprising 110 parts paraffin, 90 parts white oil and 30 parts montan wax and having a temperature of 60-70" C., and thereupon homogenizing the emulsion produced at a pressure of 150 atmospheres.

3. A method of producing impregnating substances for water-proofing textile materials,

which consists in dissolving 35 parts glue in 100 110 parts parafln, 90 parts paramn oil, and 30 parts water and emulsifying therein 6 parts of parts montan wax, and thereupon homog a. semi-drying fatty acid and adding a. solution the emulsion produced at a. temperature of 55' containing 2 parts potassium hydroxide, water, to 70 centigrade and a. pressure of at least 150 and 200 parts of a formate of a metal selected tmosphere from the group consisting of aluminum, mag- RUDOLF KERN. nesium, zinc, lead, and copper, adding thereto 

